CN112812274A - Epoxy resin with anti-silver-streak property for photocuring solder resist coating and preparation method thereof - Google Patents

Epoxy resin with anti-silver-streak property for photocuring solder resist coating and preparation method thereof Download PDF

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CN112812274A
CN112812274A CN202011608223.8A CN202011608223A CN112812274A CN 112812274 A CN112812274 A CN 112812274A CN 202011608223 A CN202011608223 A CN 202011608223A CN 112812274 A CN112812274 A CN 112812274A
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epoxy resin
anhydride
photocuring
succinic anhydride
alkali
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李明辉
李博文
张军华
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Heshan Yanmo Technology Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/14—Polycondensates modified by chemical after-treatment
    • C08G59/1433—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds
    • C08G59/1438—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds containing oxygen
    • C08G59/1455—Monocarboxylic acids, anhydrides, halides, or low-molecular-weight esters thereof
    • C08G59/1461—Unsaturated monoacids
    • C08G59/1466—Acrylic or methacrylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/14—Polycondensates modified by chemical after-treatment
    • C08G59/1494—Polycondensates modified by chemical after-treatment followed by a further chemical treatment thereof
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
    • C09D163/10—Epoxy resins modified by unsaturated compounds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
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    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend

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Abstract

The invention provides an epoxy resin for a light-cured solder mask coating with anti-crazing property and a preparation method thereof, and provides a light-cured solder mask coating with anti-crazing property prepared by using the epoxy resin and a preparation method thereof. The invention is obtained by introducing acrylic acid into epoxy resin through ring-opening reaction, then carrying out esterification reaction on hydroxyl groups of the epoxy resin and long aliphatic chain anhydride, and introducing the long chain anhydride into the reaction of hydroxyl and anhydride in the second step, thereby providing flexibility for a system, enhancing chain segment movement, reducing the glass transition temperature of a polymer, and achieving the purposes of reducing silver streak development or enabling the silver streak to retract and disappear by easy treatment. Meanwhile, the performances of weather resistance, low temperature resistance, impact strength, fatigue strength and the like of the cured material of the coating are enhanced, the application field of the solder resist photocureable coating is widened, and the requirements of the current photocureable industry on the solder resist coating are met.

Description

Epoxy resin with anti-silver-streak property for photocuring solder resist coating and preparation method thereof
Technical Field
The invention belongs to the technical field of photocuring solder resist coatings, relates to an epoxy resin with anti-silver streak performance for photocuring solder resist coatings and a preparation method thereof, and particularly aims at the preparation of photocuring coatings applied to printed wiring boards.
Background
Printed Circuit Boards (PCBs) are substrates for mounting and connecting components of modern electrical devices, and are important basic assemblies in the electronic industry.
The photocuring solder resist coating is one of key materials of a Printed Circuit Board (PCB), and is a protective coating covering a copper wire of the printed circuit, and is used for preventing the circuit from being corroded and broken, preventing short circuit between wires caused by many welding points, adjusting the adhesion amount of soldering tin, reducing the dissolved pollution of copper in the welding line, saving the soldering tin, reducing the weight of an instrument, increasing the high density of wiring, avoiding false soldering and improving the inspection speed.
The traditional photo-curing solder resist coating is generally composed of components such as a polymerization monomer, a photoinitiator, a polymerization inhibitor and the like. Currently, most of solder resists are photo-curable solder resists, which generally include a combination of a photo-polymerization initiator and a photo-curable and thermosetting resin having a carboxyl group. Among them, the photocurable and thermosetting resin is generally epoxy acrylic resin, although it has the advantages of good photocurability, developability and mechanical properties. However, in the course of curing and forming such products, due to the influence of the action of solvent, ultraviolet light, mechanical force, internal stress and the like, the cured solder mask film usually forms microcrack-like defects, namely crazes. The silver lines can be further developed under the action of larger external force, the silver lines are gradually developed to the critical size by starting from additional cavities generated by the breakage of the micro-fibers of the silver lines, then the silver lines are rapidly grown into cracks, the silver lines are continuously formed at the top ends of the cracks, and finally the material is broken and damaged. The existence of the silver veins causes the defects of brittleness, large shrinkage, low elongation, low temperature resistance, poor weather resistance and the like of a cured product, and limits the further development of the light-cured solder resist coating in many aspects.
Crazing is a morphological feature that is characteristic of polymers. The polymer appears in the defect or weak position of the material under the action of tensile stress, and the long strip-shaped fine groove is vertical to the main stress direction, and shows silvery white gloss under the irradiation of light. It has a width of about 10 μm, a thickness of 0.1-0.5 μm and a length of about 100 μm. However, unlike conventional crack defects, crazing is reversible and can be retracted and extinguished upon annealing above the stress or glass transition temperature, but annealing is generally only applicable to crazing resistant processes for organic glass-based polymers.
At present, in order to solve the crazing defect of polymers, especially epoxy resin polymers, researchers introduce an external phase into an epoxy phase according to a crazing-nail anchoring mechanism, wherein the external phase can be blocked on a fracture surface like a bridge in an epoxy resin matrix, and the external phase plays a role in preventing cracks and crazing extension caused by stress. Meanwhile, the two ends of the silver veins can be connected, and the silver veins are branched or passivated, so that the further expansion of the silver veins is prevented. In the prior art, in order to realize the mechanism, a rubber toughening process is usually adopted, a rubber elastomer is usually used for toughening epoxy resin, and the rubber for toughening epoxy resin at present is generally liquid rubber with active terminal groups, for example, in the preparation and performance research of epoxy resin electronic packaging material (trexate) in the master's academic thesis of harbinging university, carboxyl-terminated butadiene-acrylonitrile rubber is selected as a toughening agent, the shear tensile strength of epoxy resin is greatly improved along with the addition of CTBN, the microstructure of the material is observed by adopting a scanning electron microscope, the fracture mode of epoxy resin along with the addition of CTBN is changed from brittle fracture to ductile fracture, and the problem of cracking of the material can be effectively solved by the silver line effect.
However, the introduction of the active rubber toughening agent generally changes a homogeneous system of an epoxy resin cured product into a heterogeneous system, and the toughening agent aggregates to form spherical particles in a curing reaction with the epoxy resin to form a dispersed phase in a continuous phase formed by crosslinked grids of the epoxy resin, thereby achieving the purpose of toughening. Therefore, the method causes the system to be changed into a heterogeneous structure, cannot radically change the flexibility and the silver streak development resistance of the system, and can cause the phenomena of nonuniform dispersion of the system, phase separation in long-term storage and difficult uniform film formation in film coating in the use process. Secondly, the PCB is processed by lead soldering process at 260 ℃ or above, so that the light-cured solder resist coating mainly made of epoxy resin has high electrical insulation performance and can resist soldering heat treatment. However, it is difficult to achieve such a high heat-resistant temperature with the active rubber generally used as a toughening agent, so that the solder resist coating toughened with the active rubber has a limited application in the market.
In summary, in order to effectively improve the anti-crazing property of the existing photo-curable solder mask coating and further improve the mechanical toughness of the photo-cured solder mask film, a photo-curable solder mask coating with anti-crazing property is urgently needed.
Disclosure of Invention
The invention provides an epoxy resin for a light-cured solder mask coating with anti-silver streaks and a preparation method thereof according to the defects of the prior art, and provides a light-cured solder mask coating with anti-silver streaks and a preparation method thereof, wherein the light-cured solder mask coating is prepared by using the epoxy resin. According to the invention, the limited long fatty chain anhydride is introduced into the epoxy resin system, so that the flexibility is provided for the system, the chain motion is enhanced, the glass transition temperature of the polymer is reduced, and the purposes of reducing the development of silver streaks or enabling the silver streaks to retract and disappear by easy treatment are achieved; meanwhile, carboxyl groups can be introduced into a system by using the epoxy resin polymerization monomer modified by using anhydride as a raw material, so that the product has good alkali developability; in addition, the polymerized monomer takes epoxy acrylic resin as a substrate, the high-activity acrylate double bond of the polymerized monomer enables the product to keep better photosensitivity, the high double bond content ensures the crosslinking density of the product, and the cured product has good heat resistance, higher hardness and excellent chemical resistance, and is particularly suitable for being used as a solder-resistant photocuring coating and photocuring (or plating-resistant) ink.
In order to achieve the purpose, the invention adopts the technical scheme formed by the following technical measures.
An alkali-soluble photocuring epoxy resin with anti-silver streaking property is obtained by introducing acrylic acid into the epoxy resin through a ring-opening reaction, and then carrying out an esterification reaction on a hydroxyl group of the epoxy resin and long aliphatic chain anhydride;
wherein the long fatty chain anhydride is at least one of dodecenyl succinic anhydride (DDSA), N-decenyl succinic anhydride, 2-decenyl succinic anhydride, N-decyl succinic anhydride, 3-eicosenyl succinic anhydride and N-hexadecyl succinic anhydride.
The epoxy resin is selected from epoxy resin raw materials conventionally used in the field of photocuring solder resist coatings, and comprises at least one of bisphenol A epoxy resin, phenol novolac epoxy resin, o-cresol novolac epoxy resin, p-tert-butyl phenol novolac epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, diglycidyl phthalate, diglycidyl tetrahydrophthalate, triglycidyl isocyanurate and dicycladiene epoxy. Generally speaking, the raw materials of the epoxy resin suitable for the photo-curing solder resist coating can be selected from the epoxy resin of the invention.
Furthermore, in order to enable the product to have certain fluidity and higher grafting ratio, the epoxy resin is selected from the epoxy resins with the viscosity of 700-20000 mPa-s and the epoxy equivalent of 180-280 g/eq at 25 ℃.
It is noted that, because of the limitations of the photocuring property and the solder resist function of the photocuring solder resist coating, the addition ratio of the epoxy resin, the acrylic acid and the long aliphatic chain anhydride as the anhydride in the invention is consistent with the conventional ratio of the epoxy resin, the acrylic acid and the anhydride in the prior art, thereby obtaining better photocuring performance and solder resist performance.
For better illustration of the invention and to provide a reference formulation scheme, the molar amount of the epoxy resin: molar amount of acrylic acid: the molar weight of the long aliphatic chain anhydride is (0.5-1.5): 1: (0.5 to 1.5).
It is worth to be noted that, the preparation process of the alkali-soluble photocuring epoxy resin with anti-crazing property can refer to the conventional preparation process and conditions of the existing alkali-soluble photocuring epoxy resin, in order to better illustrate the present invention, and to provide a more suitable preparation method, the preparation method of the alkali-soluble photocuring epoxy resin with anti-crazing property comprises the following steps:
(1) preheating a solvent to 70-90 ℃ under the protection of inert gas, adding epoxy resin to dissolve the epoxy resin, cooling to 50-70 ℃, adding acrylic acid, heating to 70-80 ℃, adding a cyclic ester ring-opening polymerization catalyst, adding a polymerization inhibitor, stirring and reacting for 1-2 hours at 90-110 ℃, then adjusting the temperature to 100-120 ℃, stirring and reacting for 4-10 hours until the acid value of the solution is less than 3mgKOH/g, and obtaining the photocuring epoxy acrylic resin;
(2) under the protection of inert gas, cooling the photocuring epoxy acrylic resin solution obtained in the step (1) to 70-90 ℃, adding long aliphatic chain anhydride for mixing, continuing stirring and reacting at 80-100 ℃ for 3-6 hours, and obtaining the long aliphatic chain-containing alkali-soluble photocuring epoxy resin after the reaction time is up; wherein the addition amount of the polymerization inhibitor is 0.1-0.5 wt% of the epoxy resin in the step (1).
Generally, the cyclic ester ring-opening polymerization catalyst in the step (1) is a cyclic ester ring-opening polymerization catalyst conventionally used in the art, and those skilled in the art can select and apply the catalyst according to actual situations. To better illustrate the present invention and to provide a suitable alternative for reference, the cyclic ester ring-opening polymerization catalyst is at least one of triethylamine, triethanolamine, 4-dimethylaminopyridine, tetrabutylammonium bromide, tetramethylammonium chloride, N-dimethylbenzylamine, and triphenylphosphine; and the addition amount of the cyclic ester ring-opening polymerization catalyst is 0.5-1 wt% of the epoxy resin.
Generally, the polymerization inhibitor in step (1) is a polymerization inhibitor conventionally used in the art, and those skilled in the art can select and apply the polymerization inhibitor according to actual situations. To better illustrate the invention and to provide a suitable alternative by reference, the polymerization inhibitor is at least one of hydroquinone, o-methyl hydroquinone, p-hydroxyanisole, p-benzoquinone and 2, 6-di-tert-butyl-4-methylphenol.
Generally, the solvent used in step (1) is a solvent conventionally used in the art, and the skilled person can select and apply the solvent according to actual situations. In order to better illustrate the invention and provide a suitable choice for reference, the solvent is at least one of dibasic ester high boiling point environment-friendly solvent, ethylene glycol ethyl ether acetate, diethylene glycol butyl ether acetate, propylene glycol methyl ether propionate dimethyl succinate, dimethyl glutarate, dimethyl adipate and Aromatic solvent Aromatic-150; and in the step (1), the mass of the solvent is as follows: the mass of the epoxy resin is (0.5-1): (1-2).
Generally, in order to facilitate the addition of the cyclic ester ring-opening polymerization catalyst and the long aliphatic chain anhydride, the same solvent as that used for dissolving the epoxy resin is usually selected, and the cyclic ester ring-opening polymerization catalyst and the long aliphatic chain anhydride are dissolved in advance and then added according to the steps of the technical scheme of the present invention.
Wherein, in order to ensure that the stirring reaction is sufficient, the stirring reaction is carried out under the condition that the stirring rotating speed is 150-300 rad/s.
It should be noted that the stirring reaction conditions in the above preparation method are suitable when the addition amount of the epoxy resin is 150 to 500g in a laboratory environment, and generally speaking, in an industrial process, the stirring reaction conditions need to be properly expanded to achieve the effect consistent with the present invention.
Generally, in the step (1), the solvent is preheated to 70-90 ℃, the epoxy resin is added and dissolved, the time required for dissolution and the stirring conditions required for dissolution are the same, and those skilled in the art can select a suitable dissolution mode and process conditions according to the selected epoxy resin and solvent.
The alkali-soluble photocureable epoxy resin with the anti-silver-streak property, which is obtained by the preparation method, is used as a raw material component of the photocureable solder mask coating, so that the anti-silver-streak property of the photocureable solder mask coating is endowed, and the mechanical toughness of the photocured solder mask film is improved. However, since the toughness of the solder resist film is difficult to be evaluated at the present stage, and meanwhile, no known evaluation mode is provided in the technical field, the invention compares the photocuring solder resist coating in the prior art from the side by using the glass transition temperature, the photocuring power, the thermal weight loss, the chemical resistance and the electron micrograph, and the alkali-soluble photocuring epoxy resin with the anti-silver streak property prepared by the invention has higher anti-silver streak property and good comprehensive performance when being used as a raw material component of the photocuring solder resist coating.
In order to better illustrate the invention, the invention provides a light-cured solder resist coating with anti-silver-streak property, which comprises the following components in parts by weight:
100 parts of alkali-soluble photocuring epoxy resin containing long aliphatic chains;
3-10 parts of a photoinitiator.
Further, the light-cured solder resist coating comprises the following components in parts by weight:
Figure BDA0002872385530000051
among them, in order to further improve the heat resistance, the solder resist composition includes a thermosetting resin, which is preferably a polyfunctional epoxy resin, and more preferably at least one of a novolac type epoxy resin, a biphenol type epoxy resin, a bisphenol novolac type epoxy resin, and a naphthalene type epoxy resin. In addition, a proper amount of a heat curing catalyst may be added to promote the progress of the heat curing reaction.
Wherein, the photoinitiator is a photoinitiator which is conventionally used in the technical field, and the photoinitiator can be selected and applied by the technical field according to actual situations. For a better illustration of the invention, and to provide an alternative applicable by reference, the photoinitiator comprises at least one of 2, 4, 6- (trimethylbenzoyl) diphenylphosphine oxide, 2-methyl-1- (4-methylthiophenyl) -2-morpholinyl-1-acetone, 2-hydroxy-4- (2-hydroxyethoxybenzene) -2-methyl phenylpropanone, 2-isopropyl thioxanthone (2, 4 isomers), 2-hydroxy-2-methyl-1-phenyl acetone, 1-hydroxycyclohexyl phenyl carbinol, benzoin ethyl ether, benzil dimethyl ketal, 1-hydroxyphenyl hexyl acetophenone, benzophenone/triethanolamine and benzophenone/acrylate active amine.
Among them, a reactive diluent, preferably one having an ethylenically unsaturated group in the molecule, may be added for adjusting the viscosity of the system and facilitating coating. Such a reactive diluent having an ethylenically unsaturated group in the molecule is photo-cured by irradiation with an active energy ray, making the photo-curable solder resist coating insoluble in an aqueous alkali solution or contributing to insolubilization. At least one of polyester (meth) acrylate, polyether (meth) acrylate, urethane (meth) acrylate, carbonate (meth) acrylate, epoxy (meth) acrylate, and hydroxyalkyl acrylate-based reactive diluents is preferable.
In order to improve the physical strength of a coating film of the photocuring solder resist coating after photocuring, the solder resist component comprises a filler, wherein the filler is a known and conventional inorganic or organic filler, preferably one or more of titanium dioxide, bentonite, barium sulfate, spherical silica, nano calcium carbonate and talc, and further preferably a known and conventional metal oxide is simultaneously used as the filler and the pigment.
The additive is one or a combination of a plurality of pigments, a thermal polymerization inhibitor, a tackifier, a defoaming agent, a flatting agent, a coupling agent, an antioxidant and an antirust agent. Conventionally, the above pigments, thermal polymerization inhibitors, tackifiers, defoamers, leveling agents, coupling agents, antioxidants and rust inhibitors are known and used conventionally.
When the above-mentioned photocurable solder resist coating is used, it is applied to a substrate, dried appropriately (about 60 to 120 ℃), exposed to light through a pattern film or the like to obtain a cured coating film, and the unexposed portion is developed. In the development, solvent development may be carried out using the above-mentioned solvent or a known and conventional halogen-based solvent such as trichloroethylene, but alkali development is preferably carried out because a carboxyl group is introduced into the acid-modified epoxy acrylate and an unexposed portion is dissolved in an alkali aqueous solution. The alkaline solvent development can be selected from alkali metal compounds, such as sodium carbonate, potassium carbonate, sodium hydroxide, potassium hydroxide, etc.; alkaline earth metal compounds such as calcium hydroxide, etc. can also be selected; alkaline solution ammonia water can also be selected; water-soluble organic amines such as monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, monopropylamine, dipropylamine, dimethylpropylamine, monoethanolamine, diethanolamine, triethanolamine, ethylenediamine, diethylenetriamine, dimethylaminoethyl methacrylate, polyethyleneimine and the like can also be selected.
After the development, the photo-cured coating film is preferably further thermally cured by heat treatment at about 140 to 200 ℃.
In general, the photocurable solder resist coating material can be used in a state of having a dry film of a solder resist layer formed by coating and drying a thin film of PET or the like in advance, in addition to a method of directly applying the coating material to a substrate in a liquid state.
The invention has the following beneficial effects:
according to the scheme, long-chain aliphatic anhydride is used for modifying epoxy acrylic resin, and the long-chain anhydride is introduced in the second step of reaction of hydroxyl and anhydride, so that flexibility is provided for a system, chain segment movement is enhanced, the glass transition temperature of a polymer is reduced, and the purposes of reducing silver streak development or enabling the silver streak to retract and disappear by easy treatment can be achieved. Meanwhile, the performances of weather resistance, low temperature resistance, impact strength, fatigue strength and the like of the cured material of the coating are enhanced, the application field of the solder resist photocureable coating is widened, and the requirements of the current photocureable industry on the solder resist coating are met;
secondly, the alkali-soluble photocuring epoxy resin with the anti-crazing property only relates to two esterification reactions in the synthesis process, the reaction degree of each step is very high, and the influence of the related side reaction is very small, so that the overall quality of the product is improved;
the scheme of the invention utilizes a chemical method to introduce a long branched chain structure into a system for modification, can greatly improve the elongation at break of a substrate on the original basis, and in the process of silver streak expansion and extension, the long branched chain structure can be used as a bridge or a nail anchor to play a role in restraining and closing the silver streaks and prevent the silver streaks from further developing to cause macroscopic fracture; the technical scheme of the invention lays a new foundation for the development of the subsequent epoxy resin for the solder resist coating;
in the invention, carboxyl groups are introduced by the reaction of anhydride and hydroxyl, so that the product has good alkali developability, and can be quickly and completely separated by directly soaking in concentrated alkali liquor without damaging a base material. In addition, due to the strong polarity of the carboxyl group, the product has good adhesive force on the base material and is not easy to fall off.
The polymerized monomer adopted by the invention takes epoxy acrylic resin as a substrate, the high-activity acrylate double bond of the polymerized monomer enables the product to keep better photosensitivity, the high double bond content ensures the crosslinking density of the product, and the cured product has good heat resistance, higher hardness and excellent chemical resistance, and is particularly suitable for being used as a solder-resistant photocuring coating and photocuring (or plating-resistant) ink preparation and use.
Drawings
FIG. 1 is a photograph showing an example of an alkali-soluble photocurable epoxy resin with anti-crazing properties prepared in example 1.
FIG. 2 is a photograph of a photo-curable solder resist coating having anti-crazing properties prepared in application example 1.
FIG. 3 is a photograph of the photo-curable solder resist coating having anti-crazing properties prepared in application example 1 after curing treatment.
FIG. 4 is a graph showing the comparison of the glass transition temperatures of the photo-curable epoxy resin prepared in comparative example 1 and comparative example 2 and the alkali-soluble photo-curable epoxy resin having anti-crazing properties prepared in example 1, wherein the upper graph is comparative example 1, the middle graph is comparative example 2, and the lower graph is example 1. As can be seen from the figure, the product of comparative example 2 grafted tetrahydrophthalic anhydride has more difficult segment movement and higher glass transition temperature due to the addition of the benzene ring of the rigid group; in contrast, the product grafted with long aliphatic chain in example 1 has a significantly reduced glass transition temperature and improved system flexibility due to easier segment motion.
FIG. 5 is a graph showing the photo-curing kinetics of the alkali-soluble photo-curable epoxy resin having anti-crazing properties prepared in example 1. It is apparent that the resin has excellent photocurability, and the conversion of double bonds of the resin reaches a high level within 1 minute from the very beginning of the reaction.
FIG. 6 is a graph showing the thermogravimetric analysis of the alkali-soluble photocurable epoxy resin with anti-crazing properties prepared in example 1. Obviously, the initial decomposition temperature of the obtained product is 278 ℃, and the PCB can completely meet the lead soldering process of enduring more than 260 ℃ in the processing process, which shows that the product has excellent thermal performance.
Detailed Description
The invention is further illustrated by the following examples in conjunction with the accompanying drawings. It should be noted that the examples given are not to be construed as limiting the scope of the invention, and that those skilled in the art, on the basis of the teachings of the present invention, will be able to make numerous insubstantial modifications and adaptations of the invention without departing from its scope.
Characterizing the glass transition temperature of the product by Differential Scanning Calorimetry (DSC); the photocuring kinetics of the product is characterized by adopting an infrared-ultraviolet combined method; the thermal stability of the product was characterized by the method of thermal weight loss (TG).
1. Differential Scanning Calorimetry (DSC) test: the glass transition temperature of the EDPA cured coating is measured by a German Nachi company NETZSCH 204 type Differential Scanning Calorimeter (DSC), and the test atmosphere is N2The temperature rise rate is 10 ℃/min, and the temperature range is 20-250 ℃.
2. Fourier transform Infrared Spectroscopy (FT-IR) testing; the measurement is carried out by a Nicolet 560 type Fourier transform infrared spectrometer of Nicolet company in America, and the resolution is 4cm-1The scanning range is 400-4000 cm-1. And (5) drying the sample, and tabletting by KBr to prepare the sample.
3. An ultraviolet curing machine: UV LED area light source, Yinyujin optoelectronic technology, Inc.;
4. thermogravimetric (TGA) testing: the thermal stability of the EDPA cured coating is measured by adopting a TG 209F3 thermogravimetric analyzer of Germany NETZSCH company, the temperature range of the test is 30-800 ℃ in a nitrogen atmosphere, and the heating rate is set to be 10 ℃/min.
5. Chemical resistance test of the cured coating: solvent resistance test required reagents: absolute ethyl alcohol, 2 wt% NaOH, HCl, Na2CO3And (3) solution.
Example 1
The preparation method of the alkali-soluble photocuring epoxy resin with the anti-silver streaking property of the embodiment comprises the following steps of:
(1) under the protection of nitrogen, 113.5g of Aromatic-150 solvent is preheated to 90 ℃, 197.5g of epoxy resin NPCN-704 is added, the mixture is fully dissolved by keeping the temperature constant for 1 hour under the stirring condition, 67.7g of acrylic acid (the molar ratio of epoxy group to acrylic acid is 1: 1) is added after the temperature is reduced to 70 ℃, the temperature is raised to 80 ℃, 1.19g of triphenylphosphine which is a cyclic ester ring-opening polymerization catalyst dissolved in 2g of Aromatic-150 solvent in advance is added, 0.3g of hydroquinone which is a polymerization inhibitor is added, the mixture is stirred and reacted for 1 hour under the condition of 105 ℃, then the temperature is regulated to 115 ℃, the mixture is stirred and reacted for 9 hours under the temperature, and the photocuring epoxy acrylic resin is obtained when the acid value of the solution is less than 3 mgKOH/g;
(2) under the protection of nitrogen, cooling the photocuring epoxy acrylic resin solution obtained in the step (1) to 80 ℃, adding 250.3g of dodecenyl succinic anhydride (the molar ratio of acid to anhydride is 1: 1) dissolved in 100.0g of aromatic-150 solvent in advance, heating to 95 ℃, stirring for reaction for 3 hours, and obtaining the alkali-soluble photocuring epoxy resin containing long aliphatic chains after the reaction time is up;
and finally, stirring and reacting for 3 hours in the step (2) for adjusting the viscosity, stirring and adding 57.4g of DBE in the temperature reduction process after the reaction time is up, uniformly mixing and stirring, and taking out to obtain the varnish R-1.
Wherein the viscosity of the epoxy resin NPCN-704 at 25 ℃ is 6000mPa & s, and the epoxy equivalent is 230 g/eq.
Wherein, the dodecenyl succinic anhydride is an analytical pure reagent produced by Kyowa chemical reagent company Limited.
Example 2
The preparation method of the alkali-soluble photocuring epoxy resin with the anti-silver streaking property of the embodiment comprises the following steps of:
(1) under the protection of nitrogen, 113.5g of Aromatic-150 solvent is preheated to 90 ℃, 197.5g of epoxy resin NPCN-704 is added, the mixture is fully dissolved by keeping the temperature constant for 1 hour under the stirring condition, 67.7g of acrylic acid (the molar ratio of epoxy group to acrylic acid is 1: 1) is added after the temperature is reduced to 70 ℃, the temperature is raised to 80 ℃, 1.19g of triphenylphosphine which is a cyclic ester ring-opening polymerization catalyst dissolved in 2g of Aromatic-150 solvent in advance is added, 0.3g of hydroquinone which is a polymerization inhibitor is added, the mixture is stirred and reacted for 1 hour under the condition of 105 ℃, then the temperature is regulated to 115 ℃, the mixture is stirred and reacted for 9 hours under the temperature, and the photocuring epoxy acrylic resin is obtained when the acid value of the solution is less than 3 mgKOH/g;
(2) cooling the photocuring epoxy acrylic resin solution obtained in the step (1) to 80 ℃ under the protection of nitrogen, adding 223.8g of N-decenyl succinic anhydride (the molar ratio of acid to anhydride is 1: 1) dissolved in 100.0g of aromatic-150 solvent in advance, heating to 95 ℃, stirring for reaction for 3 hours, and obtaining the alkali-soluble photocuring epoxy resin containing long aliphatic chains after the reaction time is up;
and finally, stirring and reacting for 3 hours in the step (2) for adjusting the viscosity, stirring and adding 57.4g of DBE in the temperature reduction process after the reaction time is up, uniformly mixing and stirring, and taking out to obtain the R-2 varnish.
Wherein the viscosity of the epoxy resin NPCN-704 at 25 ℃ is 6000mPa & s, and the epoxy equivalent is 230 g/eq.
Wherein the N-decenyl succinic anhydride is an analytical pure reagent produced by Beijing Bailingwei science and technology Limited.
Example 3
The preparation method of the alkali-soluble photocuring epoxy resin with the anti-silver streaking property of the embodiment comprises the following steps of:
(1) under the protection of nitrogen, 113.5g of Aromatic-150 solvent is preheated to 90 ℃, 197.5g of epoxy resin NPCN-704 is added, the mixture is fully dissolved by keeping the temperature constant for 1 hour under the stirring condition, 67.7g of acrylic acid (the molar ratio of epoxy group to acrylic acid is 1: 1) is added after the temperature is reduced to 70 ℃, the temperature is raised to 80 ℃, 1.19g of triphenylphosphine which is a cyclic ester ring-opening polymerization catalyst dissolved in 2g of Aromatic-150 solvent in advance is added, 0.3g of hydroquinone which is a polymerization inhibitor is added, the mixture is stirred and reacted for 1 hour under the condition of 105 ℃, then the temperature is regulated to 115 ℃, the mixture is stirred and reacted for 9 hours under the temperature, and the photocuring epoxy acrylic resin is obtained when the acid value of the solution is less than 3 mgKOH/g;
(2) under the protection of nitrogen, cooling the photocuring epoxy acrylic resin solution obtained in the step (1) to 80 ℃, adding 225.7g of N-decyl succinic anhydride (the molar ratio of acid to acid anhydride is 1: 1) dissolved in 100.0g of aromatic-150 solvent in advance, heating to 95 ℃, stirring for reaction for 3 hours, and obtaining the alkali-soluble photocuring epoxy resin containing long aliphatic chains after the reaction time is up;
and finally, stirring and reacting for 3 hours in the step (2) for adjusting the viscosity, stirring and adding 57.4g of DBE in the temperature reduction process after the reaction time is up, uniformly mixing and stirring, and taking out to obtain the R-3 varnish.
Wherein the viscosity of the epoxy resin NPCN-704 at 25 ℃ is 6000mPa & s, and the epoxy equivalent is 230 g/eq.
Wherein the N-decyl succinic anhydride is an analytical pure reagent produced by Beijing Bailingwei science and technology Limited.
Example 4
The preparation method of the alkali-soluble photocuring epoxy resin with the anti-silver streaking property of the embodiment comprises the following steps of:
(1) under the protection of nitrogen, 113.5g of Aromatic-150 solvent is preheated to 90 ℃, 197.5g of epoxy resin NPCN-704 is added, the mixture is fully dissolved by keeping the temperature constant for 1 hour under the stirring condition, 67.7g of acrylic acid (the molar ratio of epoxy group to acrylic acid is 1: 1) is added after the temperature is reduced to 70 ℃, the temperature is raised to 80 ℃, 1.19g of triphenylphosphine which is a cyclic ester ring-opening polymerization catalyst dissolved in 2g of Aromatic-150 solvent in advance is added, 0.3g of hydroquinone which is a polymerization inhibitor is added, the mixture is stirred and reacted for 1 hour under the condition of 105 ℃, then the temperature is regulated to 115 ℃, the mixture is stirred and reacted for 9 hours under the temperature, and the photocuring epoxy acrylic resin is obtained when the acid value of the solution is less than 3 mgKOH/g;
(2) under the protection of nitrogen, cooling the photocuring epoxy acrylic resin solution obtained in the step (1) to 80 ℃, adding 304.7g of n-hexadecyl succinic anhydride (the molar ratio of acid to anhydride is 1: 1) dissolved in 100.0g of aromatic-150 solvent in advance, heating to 95 ℃, stirring for reaction for 3 hours, and obtaining the alkali-soluble photocuring epoxy resin containing long aliphatic chains after the reaction time is up;
and finally, stirring and reacting for 3 hours in the step (2) for adjusting the viscosity, stirring and adding 57.4g of DBE in the temperature reduction process after the reaction time is up, uniformly mixing and stirring, and taking out to obtain the varnish R-4.
Wherein the viscosity of the epoxy resin NPCN-704 at 25 ℃ is 6000mPa & s, and the epoxy equivalent is 230 g/eq.
Wherein the n-hexadecyl succinic anhydride is an analytically pure reagent produced by Shanghai Michell chemical technology, Inc.
Example 5
The preparation method of the alkali-soluble photocuring epoxy resin with the anti-silver streaking property of the embodiment comprises the following steps of:
(1) under the protection of nitrogen, 113.5g of diethylene glycol ethyl ether acetate solvent is preheated to 90 ℃, 197.5g of epoxy resin NPCN-638-L is added, the mixture is fully dissolved by keeping the temperature constant for 1 hour under the stirring condition, 45.2g of acrylic acid (the molar ratio of epoxy group to acrylic acid is 1.5: 1) is added after the temperature is reduced to 70 ℃, then the temperature is increased to 80 ℃, 1.19g of triphenylphosphine which is a cyclic ester ring-opening polymerization catalyst dissolved in 2g of Aromatic-150 solvent in advance is added, 0.3g of hydroquinone which is a polymerization inhibitor is added, the mixture is stirred and reacted for 2 hours under the condition of 110 ℃, then the temperature is adjusted to 120 ℃, the temperature is kept, and the stirring and reaction are carried out for 10 hours until the acid value of the solution is less than 3mgKOH/g, and the photocuring epoxy acrylic resin;
(2) under the protection of nitrogen, cooling the photocuring epoxy acrylic resin solution obtained in the step (1) to 90 ℃, adding 223.5g of 2-decaene succinic anhydride (the molar ratio of acid to acid anhydride is 1: 1.5) dissolved in 100.0g of aromatic-150 solvent in advance, continuing stirring and reacting for 6 hours at 100 ℃, and obtaining the alkali-soluble photocuring epoxy resin containing long aliphatic chains after the reaction time is up;
and finally, stirring and reacting for 3 hours in the step (2) for adjusting the viscosity, stirring and adding 57.4g of DBE in the temperature reduction process after the reaction time is up, uniformly mixing and stirring, and taking out to obtain the varnish R-5.
Wherein the viscosity of the epoxy resin NPCN-638-L at 25 ℃ is 9000 mPas, and the epoxy equivalent is 210 g/eq.
Wherein the 2-decaene succinic anhydride is prepared from analytically pure reagent produced by Shanghai Michelle chemical technology Co.
Example 6
The preparation method of the alkali-soluble photocuring epoxy resin with the anti-silver streaking property of the embodiment comprises the following steps of:
(1) under the protection of nitrogen, 113.5g of diethylene glycol ethyl ether acetate solvent is preheated to 70 ℃, 197.5g of epoxy resin NPCN-638-L is added, the mixture is fully dissolved by keeping the temperature constant for 1 hour under the stirring condition, 135.4g of acrylic acid (the molar ratio of epoxy group to acrylic acid is 0.5: 1) is added after the temperature is reduced to 50 ℃, then the temperature is increased to 70 ℃, 1.19g of triphenylphosphine which is a cyclic ester ring-opening polymerization catalyst dissolved in 2g of Aromatic-150 solvent in advance is added, 0.3g of hydroquinone which is a polymerization inhibitor is added, the mixture is stirred and reacted for 1 hour under the condition of 90 ℃, then the temperature is adjusted to 100 ℃, the temperature is kept, and the stirring and the reaction are carried out for 4 hours until the acid value of the solution is less than 3mgKOH/g, and the photocuring epoxy acrylic;
(2) under the protection of nitrogen, cooling the photocuring epoxy acrylic resin solution obtained in the step (1) to 70 ℃, adding 355.5g of 3-eicosenyl succinic anhydride (the molar ratio of acid to anhydride is 1: 0.5) dissolved in 100.0g of aromatic-150 solvent in advance, continuing stirring and reacting at 80 ℃ for 3 hours, and obtaining the alkali-soluble photocuring epoxy resin containing long aliphatic chains after the reaction time is up;
and finally, stirring and reacting for 3 hours in the step (2) for adjusting the viscosity, stirring and adding 57.4g of DBE in the temperature reduction process after the reaction time is up, uniformly mixing and stirring, and taking out to obtain the varnish R-6.
Wherein the viscosity of the epoxy resin NPCN-638-L at 25 ℃ is 9000 mPas, and the epoxy equivalent is 210 g/eq.
Wherein the 3-eicosenyl succinic anhydride is an analytically pure reagent produced by Shanghai Michelle chemical technology Co.
Comparative example 1
Under the protection of nitrogen, 113.5g of Aromatic-150 solvent is preheated to 90 ℃, 197.5g of epoxy resin NPCN-704 is added, the mixture is fully dissolved by keeping the temperature constant for 1 hour under the stirring condition, 67.7g of acrylic acid (the molar ratio of epoxy group to acrylic acid is 1: 1) is added after the temperature is reduced to 70 ℃, the temperature is raised to 80 ℃, 1.19g of triphenylphosphine which is a cyclic ester ring-opening polymerization catalyst dissolved in 2g of Aromatic-150 solvent in advance is added, 0.3g of hydroquinone which is a polymerization inhibitor is added, the mixture is stirred and reacted for 1 hour under the condition of 105 ℃, then the temperature is regulated to 115 ℃, the mixture is stirred and reacted for 9 hours under the temperature, and the photocuring epoxy acrylic resin is obtained when the acid value of the solution is less than 3 mgKOH/g;
and finally, stirring and reacting for 3 hours in the step (2) for adjusting the viscosity, stirring and adding 57.4g of DBE in the temperature reduction process after the reaction time is up, uniformly mixing and stirring, and taking out to obtain the varnish A-1.
Wherein the viscosity of the epoxy resin NPCN-704 at 25 ℃ is 6000mPa & s, and the epoxy equivalent is 230 g/eq.
Comparative example 2
(1) Under the protection of nitrogen, 113.5g of Aromatic-150 solvent is preheated to 90 ℃, 197.5g of epoxy resin NPCN-704 is added, the mixture is fully dissolved by keeping the temperature constant for 1 hour under the stirring condition, 67.7g of acrylic acid (the molar ratio of epoxy group to acrylic acid is 1: 1) is added after the temperature is reduced to 70 ℃, the temperature is raised to 80 ℃, 1.19g of triphenylphosphine which is a cyclic ester ring-opening polymerization catalyst dissolved in 2g of Aromatic-150 solvent in advance is added, 0.3g of hydroquinone which is a polymerization inhibitor is added, the mixture is stirred and reacted for 1 hour under the condition of 105 ℃, then the temperature is regulated to 115 ℃, the mixture is stirred and reacted for 9 hours under the temperature, and the photocuring epoxy acrylic resin is obtained when the acid value of the solution is less than 3 mgKOH/g;
(2) under the protection of nitrogen, cooling the photocuring epoxy acrylic resin solution obtained in the step (1) to 80 ℃, adding 142.9g (the molar ratio of acid to acid anhydride is 1: 1) of tetrahydrophthalic anhydride dissolved in 100.0g of aromatic-150 solvent in advance, heating to 95 ℃, stirring and reacting for 3 hours, and obtaining the alkali-soluble photocuring epoxy resin containing long aliphatic chains after the reaction time is up;
and finally, stirring and reacting for 3 hours in the step (2) for adjusting the viscosity, stirring and adding 57.4g of DBE in the temperature reduction process after the reaction time is up, uniformly mixing and stirring, and taking out to obtain the varnish A-2.
Wherein the viscosity of the epoxy resin NPCN-704 at 25 ℃ is 6000mPa & s, and the epoxy equivalent is 230 g/eq.
Wherein the tetrahydrophthalic anhydride is an analytical pure reagent produced by Kyowa chemical reagent Co.
Application example 1
The application example uses the alkali-soluble light-cured epoxy resin prepared in the example 1 as a raw material component of the light-cured solder resist coating, and comprises the following components in parts by weight:
100 parts of alkali-soluble light-cured epoxy resin (R-1 varnish) containing long aliphatic chains;
4 parts of 2-methyl-1- (4-methylthiophenyl) -2-morpholine-1-acetone.
The components are premixed in a stirrer, and then are milled and mixed by a three-roll mill to prepare the alkali development type photocuring solder resist coating.
The photo-curing solder resist coating after curing treatment is subjected to chemical resistance test, and the results are shown in the following table:
TABLE 1 chemical resistance
Figure BDA0002872385530000141
A is not affected, B is tarnished, adhesive and weight
Application example 2
The application example is that the alkali-soluble light-cured epoxy resin prepared in the example 2 is used as a raw material component of the light-cured solder resist coating, and comprises the following components in parts by weight:
Figure BDA0002872385530000142
Figure BDA0002872385530000151
again, in the application example, because it is difficult to evaluate the toughness of the solder resist film at the present stage, and at the same time, no known evaluation method is available in the technical field, the invention compares the photocuring solder resist coating in the prior art by the glass transition temperature, photocuring power, thermal weight loss, chemical resistance and electron microscope photos, and the alkali-soluble photocuring epoxy resin with anti-silver streaks prepared in example 1 has higher anti-silver streaks and good comprehensive performance when used as a raw material component of the photocuring solder resist coating.

Claims (10)

1. An alkali-soluble photocuring epoxy resin with anti-silver streaking property is characterized in that acrylic acid is introduced into the epoxy resin through a ring-opening reaction, and then a hydroxyl group of the epoxy resin and long aliphatic chain anhydride are subjected to an esterification reaction to obtain the epoxy resin;
wherein the long fatty chain anhydride is at least one of dodecenyl succinic anhydride, N-decenyl succinic anhydride, 2-decenyl succinic anhydride, N-decyl succinic anhydride, 3-eicosenyl succinic anhydride and N-hexadecyl succinic anhydride.
2. The alkali-soluble photocurable epoxy resin according to claim 1, wherein: the epoxy resin comprises at least one of bisphenol A epoxy resin, phenol novolac epoxy resin, o-cresol novolac epoxy resin, p-tert-butyl phenol novolac epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, diglycidyl phthalate, diglycidyl tetrahydrophthalate, triglycidyl isocyanurate and dicyclodiene epoxide.
3. The alkali-soluble photocurable epoxy resin according to claim 1 or 2, characterized in that: the epoxy resin is selected from those having a viscosity of 700 to 20000mPa s at 25 ℃ and an epoxy equivalent of 180 to 280 g/eq.
4. A preparation method of alkali-soluble photocuring epoxy resin with anti-silver streaking performance is characterized by comprising the following steps:
(1) preheating a solvent to 70-90 ℃ under the protection of inert gas, adding epoxy resin to dissolve the epoxy resin, cooling to 50-70 ℃, adding acrylic acid, heating to 70-80 ℃, adding a cyclic ester ring-opening polymerization catalyst, adding a polymerization inhibitor, stirring and reacting for 1-2 hours at 90-110 ℃, then adjusting the temperature to 100-120 ℃, stirring and reacting for 4-10 hours until the acid value of the solution is less than 3mgKOH/g, and obtaining the photocuring epoxy acrylic resin;
(2) under the protection of inert gas, cooling the photocuring epoxy acrylic resin solution obtained in the step (1) to 70-90 ℃, adding long aliphatic chain anhydride for mixing, continuing stirring and reacting at 80-100 ℃ for 3-6 hours, and obtaining the long aliphatic chain-containing alkali-soluble photocuring epoxy resin after the reaction time is up; wherein the addition amount of the polymerization inhibitor is 0.1-0.5 wt% of the epoxy resin in the step (1);
wherein the long fatty chain anhydride is at least one of dodecenyl succinic anhydride, N-decenyl succinic anhydride, 2-decenyl succinic anhydride, N-decyl succinic anhydride, 3-eicosenyl succinic anhydride and N-hexadecyl succinic anhydride.
5. The method according to claim 4, wherein: the catalyst for ring-opening polymerization of the cyclic ester in the step (1) is at least one of triethylamine, triethanolamine, 4-dimethylaminopyridine, tetrabutylammonium bromide, tetramethylammonium chloride, N-dimethylbenzylamine and triphenylphosphine; and the addition amount of the cyclic ester ring-opening polymerization catalyst is 0.5-1 wt% of the epoxy resin.
6. The method according to claim 4, wherein: in the step (1), the polymerization inhibitor is at least one of hydroquinone, o-methyl hydroquinone, p-hydroxyanisole, p-benzoquinone and 2, 6-di-tert-butyl-4-methylphenol.
7. The method according to claim 4, wherein: the solvent in the step (1) is at least one of dibasic ester high-boiling-point environment-friendly solvent, ethylene glycol ethyl ether acetate, diethylene glycol butyl ether acetate, propylene glycol methyl ether propionate dimethyl succinate, dimethyl glutarate, dimethyl adipate and Aromatic solvent Aromatic-150; and in the step (1), the mass of the solvent is as follows: the mass of the epoxy resin is (0.5-1): (1-2).
8. The method according to claim 4, wherein: molar amount of the epoxy resin: molar amount of acrylic acid: the molar weight of the long aliphatic chain anhydride is (0.5-1.5): 1: (0.5 to 1.5).
9. The method for preparing the light-cured solder mask coating with the anti-silver streaks property by using the alkali-soluble light-cured epoxy resin as described in any one of claims 1 to 3 is characterized by comprising the following components in parts by weight:
100 parts of alkali-soluble photocuring epoxy resin containing long aliphatic chains;
3-10 parts of a photoinitiator.
10. The light-curable solder resist coating according to claim 9, characterized by comprising the following components:
Figure FDA0002872385520000021
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CN114133786A (en) * 2022-01-19 2022-03-04 江苏可信电子材料有限公司 Crack-resistant solder-resist hole plugging ink and preparation method thereof
CN115651447A (en) * 2022-11-07 2023-01-31 江苏海田电子材料有限公司 High-reflectivity high-resolution white solder resist ink and production process thereof
CN115851082A (en) * 2022-12-02 2023-03-28 广东炎墨方案科技有限公司 High-oxidation-resistance solder resist coating and preparation method thereof
CN115947948A (en) * 2022-12-16 2023-04-11 广州回天新材料有限公司 Photo-curing composition and preparation method and application thereof
CN117186361A (en) * 2023-08-08 2023-12-08 广东炎墨方案科技有限公司 Adamantane modified high-heat-resistance photo-curing solder resist ink and preparation method thereof

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CN106496522A (en) * 2016-10-10 2017-03-15 中科院广州化学有限公司南雄材料生产基地 A kind of alkali solubility light-cured epoxy acrylate and preparation method and its etching resisting ink

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114133786A (en) * 2022-01-19 2022-03-04 江苏可信电子材料有限公司 Crack-resistant solder-resist hole plugging ink and preparation method thereof
CN115651447A (en) * 2022-11-07 2023-01-31 江苏海田电子材料有限公司 High-reflectivity high-resolution white solder resist ink and production process thereof
CN115651447B (en) * 2022-11-07 2023-08-11 江苏海田电子材料有限公司 High-reflectivity high-resolution white solder resist ink and production process thereof
CN115851082A (en) * 2022-12-02 2023-03-28 广东炎墨方案科技有限公司 High-oxidation-resistance solder resist coating and preparation method thereof
CN115851082B (en) * 2022-12-02 2023-12-05 广东炎墨方案科技有限公司 High-oxidation-resistance solder mask coating and preparation method thereof
CN115947948A (en) * 2022-12-16 2023-04-11 广州回天新材料有限公司 Photo-curing composition and preparation method and application thereof
CN115947948B (en) * 2022-12-16 2024-03-12 广州回天新材料有限公司 Photo-curing composition and preparation method and application thereof
CN117186361A (en) * 2023-08-08 2023-12-08 广东炎墨方案科技有限公司 Adamantane modified high-heat-resistance photo-curing solder resist ink and preparation method thereof
CN117186361B (en) * 2023-08-08 2024-05-17 广东炎墨方案科技有限公司 Adamantane modified high-heat-resistance photo-curing solder resist ink and preparation method thereof

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